Exploring Degradation Mechanisms and Recent Developments in High-Nickel Layered Cathodes for Lithium Batteries

Abstract

The Ni-rich layered cathode materials LiNi_xCo_yMn_1−x−yO₂ (NCM), which have a high energy density, are crucial in the strategic formulation of next-generation high-performance lithium-ion batteries (LIBs), particularly for cathode materials with Ni ⩾ 0.9. Although advances in NCM cathodes have made them competitive in terms of capacity and cost, persistent challenges such as surface chemical instability (electrolyte-driven surface degradation) and poor mechanical integrity (lattice oxygen evolution and anisotropic microcracking) of the cathodes remain. Addressing these limitations requires coordinated strategies spanning from atomic-level dopant engineering to macroscopic electrode architectural innovations to enable viable large-scale deployment. Extensive research has been conducted on the structural instability caused by an increase in the Ni content, but a comprehensive understanding of its underlying mechanisms and effective modification strategies for next-generation nickel-rich cathodes is lacking. Hence, we provide a thorough overview of the latest findings on microstructural degradation mechanisms in Ni-rich cathodes, delve into recent effective modification strategies and cutting-edge characterization methods, and finally, examine future research directions and limitations. This review elucidates the challenges facing ultrahigh-nickel cathodes and offers new insights into promising research avenues.

Graphical Abstract

Keywords

Lithium-ion batteries / Ultrahigh-nickel cathodes / Failure mechanism / Modification strategies

References

[1] Jin HC, Xin S, Chuang CHet al. . Black phosphorus composites with engineered interfaces for high-rate high-capacity lithium storage. Science. 2020, 370: 192-197.

[2] Yan C, Jiang LL, Yao YXet al. . Nucleation and growth mechanism of anion-derived solid electrolyte interphase in rechargeable batteries. Angew. Chem.-Int. Edit.. 2021, 60: 8521-8525.

[3] Xiao BW, Sun XL. Surface and subsurface reactions of lithium transition metal oxide cathode materials: An overview of the fundamental origins and remedying approaches. Adv. Energy Mater.. 2018, 8: 1802057.

[4] Cano ZP, Banham D, Ye SYet al. . Batteries and fuel cells for emerging electric vehicle markets. Nat. Energy. 2018, 3279-289.

[5] Schmuch R, Wagner R, Hörpel Get al. . Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy. 2018, 3: 267-278.

[6] Xu GL, Liu X, Daali Aet al. . Challenges and strategies to advance high-energy nickel-rich layered lithium transition metal oxide cathodes for harsh operation. Adv. Funct. Mater.. 2020, 30: 2004748.

[7] Li WD, Erickson EM, Manthiram A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy. 2020, 526-34.

[8] Myung ST, Maglia F, Park KJet al. . Nickel-rich layered cathode materials for automotive lithium-ion batteries: achievements and perspectives. ACS Energy Lett.. 2016, 2: 196-223.

[9] Kwade A, Haselrieder W, Leithoff Ret al. . Current status and challenges for automotive battery production technologies. Nat. Energy. 2018, 3: 290-300.

[10] Xu GL, Amine R, Xu YFet al. . Insights into the structural effects of layered cathode materials for high voltage sodium-ion batteries. Energy Environ. Sci.. 2017, 10: 1677-1693.

[11] Hua WB, Wang SN, Knapp Met al. . Structural insights into the formation and voltage degradation of lithium- and manganese-rich layered oxides. Nat. Commun.. 2019, 10: 5365.

[12] Lu JY, Xu C, Dose Wet al. . Microstructures of layered Ni-rich cathodes for lithium-ion batteries. Chem. Soc. Rev.. 2024, 534707-4740.

[13] Wang LG, Liu TC, Wu TPet al. . Strain-retardant coherent perovskite phase stabilized Ni-rich cathode. Nature. 2022, 611: 61-67.

[14] Aishova A, Park GT, Yoon CSet al. . Cobalt-free high-capacity Ni-rich layered Li[Ni_0.9Mn_0.1]O₂ cathode. Adv. Energy Mater.. 2019, 10: 1903179.

[15] Sun HH, Kim UH, Park JHet al. . Transition metal-doped Ni-rich layered cathode materials for durable Li-ion batteries. Nat. Commun.. 2021, 126552.

[16] Kim UH, Park GT, Son BKet al. . Heuristic solution for achieving long-term cycle stability for Ni-rich layered cathodes at full depth of discharge. Nat. Energy. 2020, 5860-869.

[17] Park NY, Ryu HH, Park GTet al. . Optimized Ni-rich NCMA cathode for electric vehicle batteries. Adv. Energy Mater.. 2021, 11: 2003767.

[18] Thien Nguyen T, Kim UH, Yoon CSet al. . Enhanced cycling stability of Sn-doped Li [Ni_0.90Co_0.05Mn_0.05] O₂ Via optimization of particle shape and orientation. Chem. Eng. J.. 2021, 405. 126887

[19] Kim UH, Ryu HH, Kim JHet al. . Microstructure-controlled Ni-rich cathode material by microscale compositional partition for next-generation electric vehicles. Adv. Energy Mater.. 2019, 91803902.

[20] Sun HH, Dolocan A, Weeks JAet al. . Stabilization of a highly Ni-rich layered oxide cathode through flower-petal grain arrays. ACS Nano. 2020, 1417142-17150.

[21] Ryu HH, Park KJ, Yoon DRet al. . Li [Ni_0.9Co_0.09W_0.01]O₂: a new type of layered oxide cathode with high cycling stability. Adv. Energy Mater.. 2019, 9: 1902698.

[22] Zhu HW, Wang ZH, Chen Let al. . Strain engineering of Ni-rich cathode enables exceptional cyclability in pouch-type full cells. Adv. Mater.. 2022, 352209357.

[23] Yu HF, Zhu HW, Jiang HLet al. . Restraining the escape of lattice oxygen enables superior cyclic performance towards high-voltage Ni-rich cathodes. Natl. Sci. Rev.. 2023, 10nwac166.

[24] Lee SB, Park NY, Park GTet al. . Doping strategy in developing Ni-rich cathodes for high-performance lithium-ion batteries. ACS Energy Lett.. 2024, 9740-747.

[25] Ryu HH, Lim HW, Lee SGet al. . Near-surface reconstruction in Ni-rich layered cathodes for high-performance lithium-ion batteries. Nat. Energy. 2024, 9: 47-56.

[26] Park NY, Ryu HH, Kuo LYet al. . High-energy cathodes via precision microstructure tailoring for next-generation electric vehicles. ACS Energy Lett.. 2021, 6: 4195-4202.

[27] Ryu HH, Park NY, Noh TCet al. . Microstrain alleviation in high-energy Ni-rich NCMA cathode for long battery life. ACS Energy Lett.. 2020, 6: 216-223.

[28] Park GT, Ryu HH, Park NYet al. . Tungsten doping for stabilization of Li[Ni_0.90Co_0.05Mn_0.05]O₂ cathode for Li-ion battery at high voltage. J. Power Sources. 2019, 442. 227242

[29] Park GT, Namkoong B, Kim SBet al. . Introducing high-valence elements into cobalt-free layered cathodes for practical lithium-ion batteries. Nat. Energy. 2022, 7: 946-954.

[30] Park GT, Sun HH, Noh TCet al. . Nanostructured co-free layered oxide cathode that affords fast-charging lithium-ion batteries for electric vehicles. Adv. Energy Mater.. 2022, 12: 2202719.

[31] Sheng H, Meng XH, Xiao DDet al. . An air-stable high-nickel cathode with reinforced electrochemical performance enabled by convertible amorphous Li₂CO₃ modification. Adv. Mater.. 2022, 342108947.

[32] Ryu HH, Park NY, Yoon DRet al. . New class of Ni-rich cathode materials Li[Ni_xCo_yB_1-x-y]O₂ for next lithium batteries. Adv. Energy Mater.. 2020, 102000495.

[33] Sun HH, Pollard TP, Borodin Oet al. . Degradation of high nickel Li-ion cathode materials induced by exposure to fully-charged state and its mitigation. Adv. Energy Mater.. 2023, 132204360.

[34] Park GT, Kim SB, Yoon JIet al. . Unraveling the new role of manganese in nano and microstructural engineering of Ni-rich layered cathode for advanced lithium-ion batteries. Adv. Energy Mater.. 2024, 142400130.

[35] Kim UH, Kuo LY, Kaghazchi Pet al. . Quaternary layered Ni-rich NCMA cathode for lithium-ion batteries. ACS Energy Lett.. 2019, 4576-582.

[36] Wang LF, Liu GC, Wang Ret al. . Regulating surface oxygen activity by perovskite-coating-stabilized ultrahigh-nickel layered oxide cathodes. Adv. Mater.. 2023, 35. e2209483

[37] Kim YS, Kim JH, Sun YKet al. . Evolution of a radially aligned microstructure in boron-doped Li[Ni_0.95Co_0.04Al_0.01]O₂ cathode particles. ACS Appl. Mater. Interfaces. 2022, 14: 17500-17508.

[38] Park NY, Park GT, Kim SBet al. . Degradation mechanism of Ni-rich cathode materials: focusing on particle interior. ACS Energy Lett.. 2022, 7: 2362-2369.

[39] Nam GW, Park N-Y, Park KJet al. . Capacity fading of Ni-rich NCA cathodes: effect of microcracking extent. ACS Energy Lett.. 2019, 4: 2995-3001.

[40] Yoon CS, Ryu HH, Park GTet al. . Extracting maximum capacity from Ni-rich Li [Ni_0.95Co_0.025Mn_0.025] O₂cathodes for high-energy-density lithium-ion batteries. J. Mater. Chem. A. 2018, 6: 4126-4132.

[41] Li ZZ, Huang X, Liang JNet al. . Element doping induced microstructural engineering enhancing the lithium storage performance of high-nickel layered cathodes. J. Energy Chem.. 2023, 77: 461-468.

[42] Kim UH, Park NY, Park GTet al. . High-energy W-doped Li [Ni_0.95Co_0.04Al_0.01]O₂ cathodes for next-generation electric vehicles. Energy Storage Mater.. 2020, 33: 399-407.

[43] Park GT, Yoon DR, Kim UHet al. . Ultrafine-grained Ni-rich layered cathode for advanced Li-ion batteries. Energy Environ. Sci.. 2021, 14: 6616-6626.

[44] Yang TH, Zhang K, Zuo YXet al. . Ultrahigh-nickel layered cathode with cycling stability for sustainable lithium-ion batteries. Nat. Sustain.. 2024, 7: 1204-1214.

[45] Kim UH, Kim JH, Hwang JYet al. . Compositionally and structurally redesigned high-energy Ni-rich layered cathode for next-generation lithium batteries. Mater. Today. 2019, 23: 26-36.

[46] Jung CH, Kim DH, Eum Det al. . New insight into microstructure engineering of Ni-rich layered oxide cathode for high performance lithium ion batteries. Adv. Funct. Mater.. 2021, 31: 2010095.

[47] Luo ZY, Hu GR, Wang WGet al. . Enhancing structural stability and electrochemical properties of co-less Ni-rich layer cathode materials by fluorine and niobium co doping. ACS Appl. Energy Mater.. 2022, 510927-10939.

[48] Zou Y, Liu GP, Zhou Ket al. . Enhanced interfacial stability of a LiNi_0.9Co_0.0.05O₂ cathode by a diboron additive. ACS Appl. Energ. Mater.. 2021, 4: 11051-11061.

[49] Kim UH, Lee SB, Park NYet al. . High-energy-density Li-ion battery reaching full charge in 12 Min. ACS Energy Lett.. 2022, 7: 3880-3888.

[50] Kim Y, Park H, Shin Ket al. . Rational design of coating ions via advantageous surface reconstruction in high-nickel layered oxide cathodes for lithium-ion batteries. Adv. Energy Mater.. 2021, 11: 2101112.

[51] Zhou PF, Zhang Z, Meng HJet al. . SiO₂-coated LiNi_0.915Co_0.075Al_0.01O₂ cathode material for rechargeable Li-ion batteries. Nanoscale. 2016, 819263-19269.

[52] Kim Y, Park H, Warner JHet al. . Unraveling the intricacies of residual lithium in high-Ni cathodes for lithium-ion batteries. ACS Energy Lett.. 2021, 6: 941-948.

[53] Brow R, Donakowski A, Mesnier Aet al. . Mechanical pulverization of co-free nickel-rich cathodes for improved high-voltage cycling of lithium-ion batteries. ACS Appl. Energy Mater.. 2022, 5: 6996-7005.

[54] Wang R, Wang J, Chen Set al. . Effectively stabilizing electrode/electrolyte interface of high-energy LiNi_0.9Co_0.1O₂// Si–C system by simple cathode surface-coating. Nano Energy. 2020, 76. 105065

[55] Ni LS, Guo RT, Fang SSet al. . Crack-free single-crystalline co-free Ni-rich LiNi_0.95Mn_0.05O₂ layered cathode. eScience. 2022, 2: 116-124.

[56] Hwang DY, Lee SH. Single-crystalline Ni-richLiNi_0.91Co_0.06Mn_0.03O₂ cathode enables durable interfacial stability for high electrochemical performances. Int. J. Energy Res.. 2021, 46: 2064-2072.

[57] Ryu HH, Namkoong B, Kim JHet al. . Capacity fading mechanisms in Ni-rich single-crystal NCM cathodes. ACS Energy Lett.. 2021, 6: 2726-2734.

[58] Gao MY, Wang YY, Cui SLet al. . Organo-soluble decanoic acid-modified Ni-rich cathode material LiNi_0.90Co_0.07Mn_0.03O₂ for lithium-ion batteries. ACS Appl. Mater. Interfaces. 2022, 14: 16348-16356.

[59] Zou KY, Xie SC, Jiang MZet al. . Insights into the precursor specific surface area for engineering co-free Ni-rich cathodes with tailorable properties. Chem. Eng. J.. 2024, 483. 149189

[60] Zhang YD, Li H, Liu JXet al. . LiNi_0.90Co_0.07Mg_0.03O₂ cathode materials with Mg-concentration gradient for rechargeable lithium-ion batteries. J. Mater. Chem. A. 2019, 7: 20958-20964.

[61] Lee SH, Sim SJ, Jin BSet al. . High performance well-developed single crystal LiNi_0.91Co_0.06Mn_0.03O₂ cathode via LiCl-NaCl flux method. Mater. Lett.. 2020, 270. 127615

[62] Dai PP, Kong XB, Yang HYet al. . Single-crystal Ni-rich layered LiNi_0.9Mn_0.1O₂ enables superior performance of co-free cathodes for lithium-ion batteries. ACS Sustainable Chem. Eng.. 2022, 10: 4381-4390.

[63] Bai HT, Yuan K, Zhang Cet al. . Advantageous surface engineering to boost single-crystal quaternary cathodes for high-energy-density lithium-ion batteries. Energy Storage Mater.. 2023, 61. 102879

[64] Tan ZL, Li YJ, Xi XMet al. . Lattice engineering to alleviate microcrack of LiNi_0.9Co_0.05Mn_0.05O₂ cathode for optimization their Li⁺ storage functionalities. Electrochim. Acta. 2022, 401. 139482

[65] Lee SH, Lee S, Jin BSet al. . Optimized electrochemical performance of Ni rich LiNi_0.91Co_0.06Mn_0.03O₂ cathodes for high-energy lithium ion batteries. Sci. Rep.. 2019, 9. 8901

[66] Wang L, Zhu BF, Xiao DDet al. . Grain morphology and microstructure control in high-stable Ni-rich layered oxide cathodes. Adv. Funct. Mater.. 2023, 33: 2212849.

[67] Zhang CF, Wan JJ, Li YXet al. . Restraining the polarization increase of Ni-rich and low-Co cathodes upon cycling by Al-doping. J. Mater. Chem. A. 2020, 86893-6901.

[68] He XY, Shen JX, Zhang Bet al. . Surface Li⁺/Ni²⁺ antisite defects construction for achieving high-voltage stable single-crystal Ni-rich cathode by anion/cation co-doping. Adv. Funct. Mater.. 2024, 34. 2401300

[69] Wang JP, Lu XB, Zhang YCet al. . Grain size regulation for balancing cycle performance and rate capability of LiNi_0.9Co_0.055Mn_0.045O₂ single crystal nickel-rich cathode materials. J. Energy Chem.. 2022, 65: 681-687.

[70] Cui ZH, Xie Q, Manthiram A. A cobalt- and manganese-free high-nickel layered oxide cathode for long-life, safer lithium-ion batteries. Adv. Energy Mater.. 2021, 11: 2102421.

[71] Yu HF, Cao YQ, Chen Let al. . Surface enrichment and diffusion enabling gradient-doping and coating of Ni-rich cathode toward Li-ion batteries. Nat. Commun.. 2021, 124564.

[72] Qi MY, Zhang SD, Guo SJet al. . Integrated surface modulation of ultrahigh Ni cathode materials for improved battery performance. Small Methods. 2023, 72300280.

[73] Liu C, Cui ZH, Manthiram A. Tuning dopant distribution for stabilizing the surface of high-nickel layered oxide cathodes for lithium-ion batteries. Adv. Energy Mater.. 2024, 142302722.

[74] Ni LS, Chen HY, Gao JQet al. . Multiscale crystal field effect for high-performance ultrahigh-Ni layered cathode. ACS Nano. 2023, 1712759-12773.

[75] Wu F, Liu N, Chen Let al. . Improving the reversibility of the H2–H3 phase transitions for layered Ni-rich oxide cathode towards retarded structural transition and enhanced cycle stability. Nano Energy. 2019, 59: 50-57.

[76] Hua WB, Zhang JL, Wang SNet al. . Long-range cationic disordering induces two distinct degradation pathways in co-free Ni-rich layered cathodes. Angew. Chem.-Int. Edit.. 2022, 62. e202214880

[77] Qiu QQ, Yuan SS, Bao Jet al. . Suppressing irreversible phase transition and enhancing electrochemical performance of Ni-rich layered cathode LiNi_0.9Co_0.05Mn_0.05O₂ by fluorine substitution. J. Energy Chem.. 2021, 61: 574-581.

[78] Liu L, Zhao Y, Jiang GHet al. . Dual-site lattice co-doping strategy regulated crystal-structure and microstructure for enhanced cycling stability of co-free Ni-rich layered cathode. Nano Res.. 2023, 16: 9250-9258.

[79] Wang W, Zhou YN, Zhang Bet al. . Optimized in situ doping strategy stabling single-crystal ultrahigh-nickel layered cathode materials. ACS Nano. 2024, 18: 8002-8016.

[80] Yu HF, Han Q, Chen Let al. . Highly-dispersed single-crystalline Ni-rich cathodes with low Li/O loss for high-power and long-life Li-ion batteries. Adv. Funct. Mater.. 2024, 34: 2410384.

[81] Lyu SQ, Yu J, Guo XHet al. . Mechanistically understanding the correlation between dynamic interface variation and stability of surface coating on the NMC811 materials. Adv. Energy Mater.. 2024, 152403270.

[82] Yao YX, Chen X, Yan Cet al. . Regulating interfacial chemistry in lithium-ion batteries by a weakly solvating electrolyte. Angew. Chem.-Int. Edit.. 2020, 604090-4097.

[83] You Y, Celio HG, Li JYet al. . Modified high-nickel cathodes with stable surface chemistry against ambient air for lithium-ion batteries. Angew. Chem.-Int. Edit.. 2018, 57: 6480-6485.

[84] Ryu HH, Park KJ, Yoon CSet al. . Capacity fading of Ni-rich Li [Ni_xCo_yMn_1–x–y]O₂ (0.6⩽x⩽0.95) cathodes for high-energy-density lithium-ion batteries: bulk or surface degradation?. Chem. Mat.. 2018, 30: 1155-1163.

[85] Bak SM, Hu EY, Zhou YNet al. . Structural changes and thermal stability of charged LiNi_xMn_yCo_zO₂ cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy. ACS Appl. Mater. Interfaces. 2014, 6: 22594-22601.

[86] Cho DH, Jo CH, Cho Wet al. . Effect of residual lithium compounds on layer Ni-rich Li [Ni_0.7Mn_0.3] O₂. J. Electrochem. Soc.. 2014, 161: A920-A926.

[87] Yeh NH, Wang FM, Khotimah Cet al. . Controlling Ni²⁺ from the surface to the bulk by a new cathode electrolyte interphase formation on a Ni-rich layered cathode in high-safe and high-energy-density lithium-ion batteries. ACS Appl. Mater. Interfaces. 2021, 13: 7355-7369.

[88] Ross GJ, Watts JF, Hill MPet al. . Surface modification of poly(vinylidene fluoride) by alkaline treatment1. The degradation mechanism. Polymer. 2000, 41: 1685-1696.

[89] Seong WM, Cho KH, Park JWet al. . Controlling residual lithium in high-nickel (>90 %) lithium layered oxides for cathodes in lithium-ion batteries. Angew. Chem.-Int. Edit.. 2020, 59: 18662-18669.

[90] Mahne N, Renfrew SE, McCloskey BDet al. . Electrochemical oxidation of lithium carbonate generates singlet oxygen. Angew. Chem.-Int. Edit.. 2018, 57: 5529-5533.

[91] Mahne N, Renfrew SE, McCloskey BDet al. . Elektrochemische oxidation von lithiumcarbonat generiert singulett-sauerstoff. Angew. Chem.. 2018, 130: 5627-5631.

[92] Renfrew SE, McCloskey BD. Residual lithium carbonate predominantly accounts for first cycle CO₂ and CO outgassing of Li-stoichiometric and Li-rich layered transition-metal oxides. J. Am. Chem. Soc.. 2017, 139: 17853-17860.

[93] Zhang YR, Katayama Y, Tatara Ret al. . Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy. Energy Environ. Sci.. 2020, 13: 183-199.

[94] Takahashi I, Kiuchi H, Ohma Aet al. . Cathode electrolyte interphase formation and electrolyte oxidation mechanism for Ni-rich cathode materials. J. Phys. Chem. C. 2020, 124: 9243-9248.

[95] Gnanaraj JS, Zinigrad E, Asraf Let al. . A detailed investigation of the thermal reactions of LiPF₆ solution in organic carbonates using ARC and DSC. J. Electrochem. Soc.. 2003, 150: A1533.

[96] Rinkel BLD, Vivek JP, Garcia-Araez Net al. . Two electrolyte decomposition pathways at nickel-rich cathode surfaces in lithium-ion batteries. Energy Environ. Sci.. 2022, 153416-3438.

[97] Agubra VA, Fergus JW. The formation and stability of the solid electrolyte interface on the graphite anode. J. Power Sources. 2014, 268: 153-162.

[98] Song YM, Kim CK, Kim KEet al. . Exploiting chemically and electrochemically reactive phosphite derivatives for high-voltage spinel LiNi_0.5Mn_1.5O₄ cathodes. J. Power Sources. 2016, 302: 22-30.

[99] Lux SF, Lucas IT, Pollak Eet al. . The mechanism of HF formation in LiPF6 based organic carbonate electrolytes. Electrochem. Commun.. 2012, 14: 47-50.

[100] Choi NS, Yeon JT, Lee YWet al. . Degradation of spinel lithium manganese oxides by low oxidation durability of LiPF6-based electrolyte at 60℃. Solid State Ion.. 2012, 219: 41-48.

[101] Xu HY, Li ZP, Liu TCet al. . Impacts of dissolved Ni²⁺ on the solid electrolyte interphase on a graphite anode. Angew. Chem.-Int. Edit.. 2022, 61. e202202894

[102] Han JG, Kim K, Lee Yet al. . Scavenging materials to stabilize LiPF₆-containing carbonate-based electrolytes for Li-ion batteries. Adv. Mater.. 2018, 31: 1804822.

[103] Ko DS, Park JH, Park Set al. . Microstructural visualization of compositional changes induced by transition metal dissolution in Ni-rich layered cathode materials by high-resolution particle analysis. Nano Energy. 2019, 56434-442.

[104] Streich D, Erk C, Guéguen Aet al. . Operando monitoring of early Ni-mediated surface reconstruction in layered lithiated Ni–Co–Mn oxides. J. Phys. Chem. C. 2017, 121: 13481-13486.

[105] Qiu L, Song Y, Zhang MKet al. . Structural reconstruction driven by oxygen vacancies in layered Ni-rich cathodes. Adv. Energy Mater.. 2022, 12: 2200022.

[106] Gao A, Li XY, Zhang QHet al. . Dynamic transition metal network via orbital population design stabilizes lattice oxygen redox in stoichiometric layered cathodes. Adv. Mater.. 2025, 37e2412673.

[107] Seo DH, Lee J, Urban Aet al. . The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem.. 2016, 8692-697.

[108] Gao X, Li B, Kummer Ket al. . Clarifying the origin of molecular O₂ in cathode oxides. Nat. Mater.. 2025, 24: 743-752.

[109] Wei ZS, Liang C, Jiang LHet al. . Probing the thermal degradation mechanism of polycrystalline and single-crystal Li(Ni_0.8Co_0.1Mn_0.1)O₂ cathodes from the perspective of oxygen vacancy diffusion. Energy Storage Mater.. 2023, 56: 495-505.

[110] Li H, Wang L, Song YZet al. . Understanding the insight mechanism of chemical-mechanical degradation of layered co-free Ni-rich cathode materials: a review. Small. 2023, 19: 2302208.

[111] Hou XY, Kimura Y, Tamenori Yet al. . Thermodynamic analysis enables quantitative evaluation of lattice oxygen stability in Li-ion battery cathodes. ACS Energy Lett.. 2022, 71687-1693.

[112] Liu X, Xu GL, Yin Let al. . Probing the thermal-driven structural and chemical degradation of Ni-rich layered cathodes by Co/Mn exchange. J. Am. Chem. Soc.. 2020, 142: 19745-19753.

[113] Jiang M, Danilov DL, Eichel RAet al. . A review of degradation mechanisms and recent achievements for Ni-rich cathode-based Li-ion batteries. Adv. Energy Mater.. 2021, 11: 2103005.

[114] Sim R, Manthiram A. Factors influencing gas evolution from high-nickel layered oxide cathodes in lithium-based batteries. Adv. Energy Mater.. 2024, 142303985.

[115] Noh HJ, Youn S, Yoon CSet al. . Comparison of the structural and electrochemical properties of layered Li [Ni_x Co_y Mn_z] O₂ (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries. J. Power Sources. 2013, 233121-130.

[116] Shah NA, Páez Fajardo GJ, Banerjee Het al. . Nature of the oxygen-loss-induced rocksalt layer and its impact on capacity fade in Ni-rich layered oxide cathodes. ACS Energy Lett.. 2025, 10: 1313-1320.

[117] Li JY, Hua HM, Kong XBet al. . In-situ probing the near-surface structural thermal stability of high-nickel layered cathode materials. Energy Storage Mater.. 2022, 46: 90-99.

[118] Hou D, Xu ZR, Yang ZJet al. . Effect of the grain arrangements on the thermal stability of polycrystalline nickel-rich lithium-based battery cathodes. Nat. Commun.. 2022, 13: 3437.

[119] Song YJ, Cui YP, Li BYet al. . Revealing the origin of high-thermal-stability of single-crystal Ni-rich cathodes toward higher-safety batteries. Nano Energy. 2023, 116. 108846

[120] Wang XQ, Ren DS, Liang HMet al. . Ni crossover catalysis: Truth of hydrogen evolution in Ni-rich cathode-based lithium-ion batteries. Energy Environ. Sci.. 2023, 161200-1209.

[121] Yin SY, Deng WT, Chen Jet al. . Fundamental and solutions of microcrack in Ni-rich layered oxide cathode materials of lithium-ion batteries. Nano Energy. 2021, 83. 105854

[122] Yang J, Liang XH, Ryu HHet al. . Ni-rich layered cathodes for lithium-ion batteries: from challenges to the future. Energy Storage Mater.. 2023, 63. 102969

[123] Guo FQR, Chen YQ, Song Yet al. . Oxygen vacancies driven by co in the deeply charged state inducing intragranular cracking of Ni-rich cathodes. Small. 2024, 20. 2310321

[124] Kondrakov AO, Geßwein H, Galdina Ket al. . Charge-transfer-induced lattice collapse in Ni-rich NCM cathode materials during delithiation. J. Phys. Chem. C. 2017, 121: 24381-24388.

[125] Kondrakov AO, Schmidt A, Xu Jet al. . Anisotropic lattice strain and mechanical degradation of high- and low-nickel NCM cathode materials for Li-ion batteries. J. Phys. Chem. C. 2017, 121: 3286-3294.

[126] Seo DH, Urban A, Ceder G. Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides. Phys. Rev. B. 2015, 92. 115118

[127] Kim, J.H., Ryu, H.H., Kim, S.J., et al.: Degradation Mechanism of Highly Ni-Rich Li[Ni_xCo_yMn_1-x-y]O₂ Cathodes with x>09. ACS Appl. Mater. Interfaces 11, 30936–30942 (2019). https://doi.org/10.1021/acsami.9b09754

[128] Park KJ, Hwang JY, Ryu HHet al. . Degradation mechanism of Ni-enriched NCA cathode for lithium batteries: are microcracks really critical?. ACS Energy Lett.. 2019, 4: 1394-1400.

[129] Li WD, Asl HY, Xie Qet al. . Collapse of LiNi_1–x–yCo_xMn_yO₂ lattice at deep charge irrespective of nickel content in lithium-ion batteries. J. Am. Chem. Soc.. 2019, 141: 5097-5101.

[130] Song SH, Cho M, Park Iet al. . High-voltage-driven surface structuring and electrochemical stabilization of Ni-rich layered cathode materials for Li rechargeable batteries. Adv. Energy Mater.. 2020, 10: 2000521.

[131] Lee SY, Park GS, Jung Cet al. . Revisiting primary particles in layered lithium transition-metal oxides and their impact on structural degradation. Adv. Sci.. 2019, 6. 1800843

[132] Ko DS, Park JH, Yu BYet al. . Degradation of high-nickel-layered oxide cathodes from surface to bulk: a comprehensive structural, chemical, and electrical analysis. Adv. Energy Mater.. 2020, 102001035.

[133] Li SF, Jiang ZS, Han JXet al. . Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides. Nat. Commun.. 2020, 11. 4433

[134] Xu C, Merryweather AJ, Pandurangi SSet al. . Operando visualization of kinetically induced lithium heterogeneities in single-particle layered Ni-rich cathodes. Joule. 2022, 62535-2546.

[135] Besli MM, Xia SH, Kuppan Set al. . Mesoscale chemomechanical interplay of the LiNi_0.8Co_0.15Al_0.05O₂ cathode in solid-state polymer batteries. Chem. Mat.. 2019, 31: 491-501.

[136] Xu ZR, Jiang ZS, Kuai CGet al. . Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials. Nat. Commun.. 2020, 11. 83

[137] Qian GN, Huang H, Hou FCet al. . Selective dopant segregation modulates mesoscale reaction kinetics in layered transition metal oxide. Nano Energy. 2021, 84. 105926

[138] Mistry A, Heenan T, Smith Ket al. . Asphericity can cause nonuniform lithium intercalation in battery active particles. ACS Energy Lett.. 2022, 7: 1871-1879.

[139] Kim JH, Kim SJ, Yuk Tet al. . Variation of electronic conductivity within secondary particles revealing a capacity-fading mechanism of layered Ni-rich cathode. ACS Energy Lett.. 2018, 3: 3002-3007.

[140] Bi YJ, Tao JH, Wu YQet al. . Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode. Science. 2020, 370: 1313-1317.

[141] Meng XH, Lin T, Mao HCet al. . Kinetic origin of planar gliding in single-crystalline Ni-rich cathodes. J. Am. Chem. Soc.. 2022, 144: 11338-11347.

[142] Wang CY, Wang XL, Zhang Ret al. . Resolving complex intralayer transition motifs in high-Ni-content layered cathode materials for lithium-ion batteries. Nat. Mater.. 2023, 22: 235-241.

[143] Wang CY, Wang XL, Zou PCet al. . Direct observation of chemomechanical stress-induced phase transformation in high-Ni layered cathodes for lithium-ion batteries. Matter. 2023, 6: 1265-1277.

[144] Eum D, Park SO, Jang HYet al. . Electrochemomechanical failure in layered oxide cathodes caused by rotational stacking faults. Nat. Mater.. 2024, 23: 1093-1099.

[145] Huang WY, Liu TC, Yu Let al. . Unrecoverable lattice rotation governs structural degradation of single-crystalline cathodes. Science. 2024, 384: 912-919.

[146] Yu ZL, Qu XY, Wan Tet al. . Synthesis and mechanism of high structural stability of nickel-rich cathode materials by adjusting Li-excess. ACS Appl. Mater. Interfaces. 2020, 12: 40393-40403.

[147] Kalyani P, Kalaiselvi N. Various aspects of LiNiO₂ chemistry: a review. Sci. Technol. Adv. Mater.. 2005, 6: 689-703.

[148] Chen WX, Muhtar D, Li KLet al. . Regulating cation disorder triggered-electronic reshuffling for sustainable conventional layered oxide cathodes. Chem. Mater.. 2024, 36: 1249-1261.

[149] Wu K, Ran PL, Yin Wet al. . Dynamic evolution of antisite defect and coupling anionic redox in high-voltage ultrahigh-Ni cathode. Angew. Chem.-Int. Edit.. 2024, 63. e202410326

[150] Liu W, Li XF, Hao YCet al. . Functional passivation interface of LiNi_0.8Co_0.1Mn_0.1O₂ toward superior lithium storage. Adv. Funct. Mater.. 2021, 31. 2008301

[151] Kim Y, Kim D, Kang S. Experimental and first-principles thermodynamic study of the formation and effects of vacancies in layered lithium nickel cobalt oxides. Chem. Mater.. 2011, 23: 5388-5397.

[152] Chernova NA, Ma MM, Xiao Jet al. . Layered Li_xNi_yMn_yCo_1−2yO₂ cathodes for lithium ion batteries: understanding local structure via magnetic properties. Chem. Mater.. 2007, 19: 4682-4693.

[153] Zheng JX, Teng GF, Xin Cet al. . Role of superexchange interaction on tuning of Ni/Li disordering in layered Li(Ni_xMn_yCo_z)O₂. J. Phys. Chem. Lett.. 2017, 8: 5537-5542.

[154] Song YJ, Cui YP, Geng Let al. . Li/Ni intermixing: the real origin of lattice oxygen stability in co-free Ni-rich cathode materials. Adv. Energy Mater.. 2023, 14: 2303207.

[155] Tang ZF, Wang S, Liao JYet al. . Facilitating lithium-ion diffusion in layered cathode materials by introducing Li⁺/Ni²⁺ antisite defects for high-rate Li-ion batteries. Research. 2019, 20192198906.

[156] Park GT, Park NY, Noh TCet al. . High-performance Ni-rich Li [Ni_0.9–xCo_0.1Al_x] O₂ cathodes via multi-stage microstructural tailoring from hydroxide precursor to the lithiated oxide. Energy Environ. Sci.. 2021, 145084-5095.

[157] Nomura Y, Yamamoto K, Yamagishi Yet al. . Lithium transport pathways guided by grain architectures in Ni-rich layered cathodes. ACS Nano. 2021, 15: 19806-19814.

[158] Xu X, Huo H, Jian JYet al. . Radially oriented single-crystal primary nanosheets enable ultrahigh rate and cycling properties of LiNi_0.8Co_0.1Mn_0.1O₂ cathode material for lithium-ion batteries. Adv. Energy Mater.. 2019, 9: 1803963.

[159] Park KJ, Jung HG, Kuo LYet al. . Improved cycling stability of Li [Ni_0.90Co_0.05Mn_0.05]O₂ through microstructure modification by boron doping for Li-ion batteries. Adv. Energy Mater.. 2018, 81801202.

[160] Ryu HH, Park NY, Seo JHet al. . A highly stabilized Ni-rich NCA cathode for high-energy lithium-ion batteries. Mater. Today. 2020, 3673-82.

[161] Kim Y, Kim H, Shin Wet al. . Insights into the microstructural engineering of cobalt-free, high-nickel cathodes based on surface energy for lithium-ion batteries. Adv. Energy Mater.. 2023, 13: 2204054.

[162] Seo JH, Kim UH, Sun YKet al. . Multi-doped (ga, B) li [Ni_0.885Co_0.100Al_0.015] O₂Cathode. J. Electrochem. Soc.. 2020, 167. 100557

[163] Li LJ, Fu LZ, Li Met al. . B-doped and La₄NiLiO₈-coated Ni-rich cathode with enhanced structural and interfacial stability for lithium-ion batteries. J. Energy Chem.. 2022, 71588-594.

[164] Namkoong B, Park NY, Park GTet al. . Hign-energy Ni-rich cathode materials for long-range and long-life alectric vehicles. Adv. Energy Mater.. 2022, 12: 2200615.

[165] Kim UH, Yu TY, Lee JWet al. . Microstructure- and interface-modified Ni-rich cathode for high-energy-density all-solid-state lithium batteries. ACS Energy Lett.. 2023, 8809-817.

[166] Park GT, Kim SB, Namkoong Bet al. . A new ternary co-free layered cathode, Li [Ni_1−x−yTi_xAl_y]O₂, for high-energy lithium-ion batteries. Mater. Today. 2023, 71: 38-49.

[167] Liang LW, Li XY, Su MSet al. . Chemomechanically stable small single-crystal Mo-doped LiNi_0.6Co_0.2Mn_0.2O₂ cathodes for practical 45 V-class pouch-type Li-ion batteries. Angew. Chem. Int. Ed.. 2023, 62: e202216155.

[168] Wang JL, Liu CJ, Wang Qet al. . Investigation of W⁶⁺-doped in high-nickel LiNi_0.83Co_0.11Mn_0.06O₂ cathode materials for high-performance lithium-ion batteries. J. Colloid Interface Sci.. 2022, 628338-349.

[169] Levartovsky Y, Chakraborty A, Kunnikuruvan Set al. . High-energy Ni-rich LiNi_0.85Co_0.1Mn_0.05O₂ cathode material for Li-ion batteries enhanced by Nd- and Y-doping. A structural, electrochemical, and thermal investigation. ACS Appl. Energy Mater.. 2022, 5: 11142-11151.

[170] Wang S, Zhou X, Zhao Tet al. . Precise regulation of particle orientation for Ni-rich cathodes with ultra-long cycle life. Nano Energy. 2024, 129. 110008

[171] Zhou X, Hong FF, Wang Set al. . Precision engineering of high-performance Ni-rich layered cathodes with radially aligned microstructure through architectural regulation of precursors. eScience. 2024, 4. 100276

[172] Allen E, Shin Y, Judge Wet al. . 3D quantification of elemental gradients within heterostructured particles of battery cathodes. ACS Energy Lett.. 2023, 8: 1371-1378.

[173] Wang LG, Lei XC, Liu TCet al. . Regulation of surface defect chemistry toward stable Ni-rich cathodes. Adv. Mater.. 2022, 34. 2200744

[174] Jing ZW, Wang SN, Fu Qet al. . Architecting “Li-rich Ni-rich” core-shell layered cathodes for high-energy Li-ion batteries. Energy Storage Mater.. 2023, 59. 102775

[175] Meng XH, Zhang XD, Sheng Het al. . Chemical-mechanical robustness of single-crystalline Ni-rich cathode enabled by surface atomic arrangement control. Angew. Chem. -Int. Edit.. 2023, 62. e202302170

[176] Li M, Lu J. Cobalt in lithium-ion batteries. Science. 2020, 367: 979-980.

[177] Kim J, Lee I, Kim YHet al. . Ni-rich cathode material with isolated porous layer hindering crack propagation under 4.5 V high cut-off voltage cycling. Chem. Eng. J.. 2023, 455. 140578

[178] Liu TC, Yu L, Liu JXet al. . Ultrastable cathodes enabled by compositional and structural dual-gradient design. Nat. Energy. 2024, 9: 1252-1263.

[179] Ji HW, Wu JP, Cai ZJet al. . Ultrahigh power and energy density in partially ordered lithium-ion cathode materials. Nat. Energy. 2020, 5: 213-221.

[180] Clément RJ, Lun Z, Ceder G. Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes. Energy Environ. Sci.. 2020, 13: 345-373.

[181] Goodenough JB, Kim Y. Challenges for rechargeable Li batteries. Chem. Mat.. 2010, 22: 587-603.

[182] Tan ZL, Li YJ, Lei CLet al. . In situ constructing ultrastable mechanical integrity of single-crystalline LiNi_0.9Co_0.05Mn_0.05O₂ cathode by interior and exterior decoration strategy. Small. 2024, 20. 2305618

[183] Zou YG, Mao HC, Meng XHet al. . Mitigating the kinetic hindrance of single-crystalline Ni-rich cathode via surface gradient penetration of tantalum. Angew. Chem. -Int. Edit.. 2021, 60: 26535-26539.

[184] Zhou WD, Huang H, Liu XHet al. . Perspective on the preparation methods of single crystalline high nickel oxide cathode materials. Adv. Energy Mater.. 2023, 13: 2300378.

[185] Wu YQ, Wu HF, Deng JSet al. . Insight of synthesis of single crystal Ni-rich LiNi_1–x–yCo_xMn_yO₂ cathodes. Adv. Energy Mater.. 2024, 142303758.

[186] Zeng CR, Zheng RX, Fan FXet al. . Phase compatible surface engineering to boost the cycling stability of single-crystalline Ni-rich cathode for high energy density lithium-ion batteries. Energy Storage Mater.. 2024, 72. 103788

[187] Liu JK, Yang XR, Wang CWet al. . Surface-to-bulk engineering with high-valence W⁶⁺ enabling stabilized single-crystal LiNi_0.9Co_0.05Mn_0.05O₂ cathode. J. Energy Chem.. 2024, 9867-76.

[188] Huang H, Zhu HJ, Gao Jet al. . Grain-growth inhibitor with three-section-sintering for highly dispersed single-crystal NCM90 cubes. Angew. Chem. -Int. Edit.. 2024, 63. e202314457

[189] Zhang, Y.J., Xue, Z.C., Hu, G.R., et al.: The grain coarsening principle and the surface degradation mechanism of single-crystalline LiNi_1-x-yCo_xMn_yO₂ in lithium-ion batteries prepared by the flux-assisted method. Chem. Eng. J. 509, 161243 (2025). https://doi.org/10.1016/j.cej.2025.161243

[190] Lv F, Zhang YM, Wu MTet al. . A molten-salt method to synthesize ultrahigh-nickel single-crystalline LiNi_0.92Co_0.06Mn_0.02O₂ with superior electrochemical performance as cathode material for lithium-ion batteries. Small. 2022, 18. 2201946

[191] Huang H, Zhang LP, Tian HYet al. . Pulse high temperature sintering to prepare single-crystal high nickel oxide cathodes with enhanced electrochemical performance. Adv. Energy Mater.. 2023, 13: 2203188.

[192] Qiu L, Zhang MK, Song Yet al. . Origin and regulation of interface fusion during synthesis of single-crystal Ni-rich cathodes. Angew. Chem.-Int. Edit.. 2023, 62. e202300209

[193] Liu JJ, Yuan YF, Zheng JHet al. . Understanding the synthesis kinetics of single-crystal co-free Ni-rich cathodes. Angew. Chem. -Int. Edit.. 2023, 62. e202302547

[194] Huang CY, Zheng HF, Qin Net al. . Single-crystal nickel-rich cathode materials: challenges and strategies. Acta Phys. -Chim. Sin.. 2024, 402308051.

[195] Yang HY, Kong XB, Li JYet al. . In-situ construction of a thermodynamically stabilized interface on the surface of single crystalline Ni-rich cathode materials via a one-step molten-salt route. Nano Res.. 2023, 166771-6779.

[196] Hu JT, Li LZ, Bi YJet al. . Locking oxygen in lattice: a quantifiable comparison of gas generation in polycrystalline and single crystal Ni-rich cathodes. Energy Storage Mater.. 2022, 47: 195-202.

[197] Fan XM, Hu GR, Zhang Bet al. . Crack-free single-crystalline Ni-rich layered NCM cathode enable superior cycling performance of lithium-ion batteries. Nano Energy. 2020, 70. 104450

[198] Sun JM, Cao X, Yang HJet al. . The origin of high-voltage stability in single-crystal layered Ni-rich cathode materials. Angew. Chem. -Int. Edit.. 2022, 61. e202207225

[199] Ryu HH, Lee SB, Yoon CSet al. . Morphology-dependent battery performance of Ni-rich layered cathodes: single-crystal versus refined polycrystal. ACS Energy Lett.. 2022, 7: 3072-3079.

[200] Yan PF, Zheng JM, Gu Met al. . Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries. Nat. Commun.. 2017, 8. 14101

[201] Han GM, Kim YS, Ryu HHet al. . Structural stability of single-crystalline Ni-rich layered cathode upon delithiation. ACS Energy Lett.. 2022, 7: 2919-2926.

[202] Trevisanello E, Ruess R, Conforto Get al. . Polycrystalline and single crystalline NCM cathode materials: Quantifying particle cracking, active surface area, and lithium diffusion. Adv. Energy Mater.. 2021, 11: 2003400.

[203] Kim M, Zhu J, Li LZet al. . Understanding reactivities of Ni-rich Li [Ni_xMn_yCo_1–x–y] O₂ single-crystal cathode materials. ACS Appl. Energy Mater.. 2020, 312238-12245.

[204] Zhu J, Sharifi-Asl S, Garcia JCet al. . Atomic-level understanding of surface reconstruction based on Li [Ni_xMn_yCo_1–x–y] O₂ single-crystal studies. ACS Appl. Energy Mater.. 2020, 3: 4799-4811.

[205] Zhang F, Lou SF, Li Set al. . Surface regulation enables high stability of single-crystal lithium-ion cathodes at high voltage. Nat. Commun.. 2020, 11. 3050

[206] Ni LS, Chen HY, Gao JQet al. . Calcium-induced pinning effect for high-performance co-free Ni-rich NMA layered cathode. Nano Energy. 2023, 115. 108743

[207] Mu LQ, Kan WH, Kuai CGet al. . Structural and electrochemical impacts of Mg/Mn dual dopants on the LiNiO₂ cathode in Li-metal batteries. ACS Appl. Mater. Interfaces. 2020, 12: 12874-12882.

[208] Gomez-Martin A, Reissig F, Frankenstein Let al. . Magnesium substitution in Ni-rich NMC layered cathodes for high-energy lithium ion batteries. Adv. Energy Mater.. 2022, 12: 2103045.

[209] Zou LF, Li JY, Liu ZYet al. . Lattice doping regulated interfacial reactions in cathode for enhanced cycling stability. Nat. Commun.. 2019, 10. 3447

[210] Wang YY, Liang ZM, Liu ZCet al. . Synergy of epitaxial layer and bulk doping enables structural rigidity of cobalt-free ultrahigh-nickel oxide cathode for lithium-ion batteries. Adv. Funct. Mater.. 2023, 33. 2308152

[211] Ou X, Liu TC, Zhong WTet al. . Enabling high energy lithium metal batteries via single-crystal Ni-rich cathode material co-doping strategy. Nat. Commun.. 2022, 132319.

[212] Jamil S, Yu RZ, Wang Qet al. . Enhanced cycling stability of nickel-rich layered oxide by tantalum doping. J. Power Sources. 2020, 473. 228597

[213] Huang W, Li WJ, Wang Let al. . Structure and charge regulation strategy enabling superior cyclability for Ni-rich layered cathode materials. Small. 2021, 172104282.

[214] Qiu ZP, Zhang YL, Liu Zet al. . Stabilizing Ni-rich LiNi_0.92Co_0.06Al_0.02O₂ cathodes by boracic polyanion and tungsten cation co-doping for high-energy lithium-ion batteries. ChemElectroChem. 2020, 73811-3817.

[215] Huang Y, Liu X, Yu RZet al. . Tellurium surface doping to enhance the structural stability and electrochemical performance of layered Ni-rich cathodes. ACS Appl. Mater. Interfaces. 2019, 11: 40022-40033.

[216] Li XL, Kang FY, Shen WCet al. . Improvement of structural stability and electrochemical activity of a cathode material LiNi_0.7Co_0.3O₂ by chlorine doping. Electrochim. Acta. 2007, 53: 1761-1765.

[217] Azhari L, Sousa B, Ahmed Ret al. . Stability enhancement and microstructural modification of Ni-rich cathodes via halide doping. ACS Appl. Mater. Interfaces. 2022, 14: 46523-46536.

[218] Zhu ZH, Liang YS, Hu Het al. . Enhanced structural and electrochemical stability of LiNi_0.83Co_0.11Mn_0.06O₂ cathodes by zirconium and aluminum co-doping for lithium-ion battery. J. Power Sources. 2021, 498. 229857

[219] Li J, Zhong WT, Deng Qet al. . Mechanistic origin for high structural stability of single crystalline nickel-rich cathode materials via Al and Sm co-doping. Adv. Funct. Mater.. 2023, 33. 2300127

[220] Wang XZ, Zuo YT, Qin YBet al. . Fast Na⁺ kinetics and suppressed voltage hysteresis enabled by a high-entropy strategy for sodium oxide cathodes. Adv. Mater.. 2024, 36. 2312300

[221] Song J, Ning FH, Zuo YXet al. . Entropy stabilization strategy for enhancing the local structural adaptability of Li-rich cathode materials. Adv. Mater.. 2023, 35. 2208726

[222] Tan XH, Zhang YX, Xu SYet al. . High-entropy surface complex stabilized LiCoO₂ cathode. Adv. Energy Mater.. 2023, 13: 2300147.

[223] Zhang R, Wang CY, Zou PCet al. . Compositionally complex doping for zero-strain zero-cobalt layered cathodes. Nature. 2022, 61067-73.

[224] Xu ZX, Chen XH, Fan WGet al. . High-entropy rock-salt surface layer stabilizes the ultrahigh-Ni single-crystal cathode. ACS Nano. 2024, 18: 33706-33717.

[225] Zhao BY, Sun X, Bi HWet al. . Design high-entropy core-shell nickel-rich cobalt-free cathode material toward high performance lithium batteries. Adv. Funct. Mater.. 2025.

[226] Liang PR, Qi KW, Chen SYet al. . Low-electronegativity cationic high-entropy doping to trigger stable anion redox activity for high-Ni co-free layered cathodes in Li-ion batteries. Angew. Chem. -Int. Edit.. 2024, 63. e202318186

[227] Zhou JH, Hu JH, Zhou Xet al. . High-entropy doping for high-performance zero-cobalt high-nickel layered cathode materials. Energy Environ. Sci.. 2025, 18: 347-353.

[228] Liang LW, Su MS, Sun ZFet al. . High-entropy doping promising ultrahigh-Ni co-free single-crystalline cathode toward commercializable high-energy lithium-ion batteries. Sci. Adv.. 2024, 10. eado4472

[229] Liu Y, Xin Y, He BJet al. . High entropy fine-tuning achieves fast Li⁺ kinetics in high-performance co-free high-Ni layered cathodes. Adv. Mater.. 2025, 37. 2417353

[230] Wu BH, Lin ZY, Zhang GGet al. . In situ mitigating cation mixing of Ni-rich cathode at high voltage via Li₂MnO₃ injection. Energy Storage Mater.. 2022, 53: 212-221.

[231] Tan XH, Chen ZF, Liu TCet al. . Imitating architectural mortise-tenon structure for stable Ni-rich layered cathodes. Adv. Mater.. 2023, 35. 2301096

[232] Park NY, Kim SB, Kim MCet al. . Mechanism of doping with high-valence elements for developing Ni-rich cathode materials. Adv. Energy Mater.. 2023, 13: 2301530.

[233] Yoon CS, Choi MJ, Jun DWet al. . Cation ordering of Zr-doped LiNiO₂ cathode for lithium-ion batteries. Chem. Mater.. 2018, 301808-1814.

[234] Lin LL, Zhang LH, Fu ZQet al. . Unraveling mechanism for microstructure engineering toward high-capacity nickel-rich cathode materials. Adv. Mater.. 2024.

[235] Kim UH, Park GT, Conlin Pet al. . Cation ordered Ni-rich layered cathode for ultra-long battery life. Energy Environ. Sci.. 2021, 14: 1573-1583.

[236] Li WW, Zhang XJ, Si JJet al. . TiO₂-coated LiNi_0.9Co_0.08Al_0.02O₂ cathode materials with enhanced cycle performance for Li-ion batteries. Rare Met.. 2021, 40: 1719-1726.

[237] Ma Y, Teo JH, Walther Fet al. . Advanced nanoparticle coatings for stabilizing layered Ni-rich oxide cathodes in solid-state batteries. Adv. Funct. Mater.. 2022, 32. 2111829

[238] Lu SQ, Zhang QH, Meng Fet al. . Surface lattice modulation through chemical delithiation toward a stable nickel-rich layered oxide cathode. J. Am. Chem. Soc.. 2023, 145: 7397-7407.

[239] Yu ZZ, Zhao GQ, Ji FLet al. . Collaboratively enhancing electrochemical properties of LiNi_0.83Co_0.11Mn_0.06O₂ through doping and coating of quadrivalent elements. Rare Met.. 2023, 42: 4103-4114.

[240] Susai FA, Sclar H, Maiti Set al. . Stabilized behavior of LiNi_0.85Co_0.10Mn_0.05O₂ cathode materials induced by their treatment with SO₂. ACS Appl. Energy Mater.. 2020, 3: 3609-3618.

[241] Qian RC, Liu YL, Cheng Tet al. . Enhanced surface chemical and structural stability of Ni-rich cathode materials by synchronous lithium-ion conductor coating for lithium-ion batteries. ACS Appl. Mater. Interfaces. 2020, 12: 13813-13823.

[242] Yang W, Xiang W, Chen YXet al. . Interfacial regulation of Ni-rich cathode materials with an ion-conductive and pillaring layer by infusing gradient boron for improved cycle stability. ACS Appl. Mater. Interfaces. 2020, 12: 10240-10251.

[243] Su YF, Chen G, Chen Let al. . Roles of fast-ion conductor LiTaO₃ modifying Ni-rich cathode material for Li-ion batteries. Chemsuschem. 2021, 14: 1955-1961.

[244] Sun YJ, Wang CH, Huang WJet al. . One-step calcination synthesis of bulk-doped surface-modified Ni-rich cathodes with superlattice for long-cycling Li-ion batteries. Angew. Chem. -Int. Edit.. 2023, 62. e202300962

[245] Sun YJ, Huang WJ, Zhao GFet al. . LiNi_0.9Co_0.09Mo_0.01O₂ cathode with Li₃PO₄ coating and Ti doping for next-generation lithium-ion batteries. ACS Energy Lett.. 2023, 8: 1629-1638.

[246] Ryu HH, Lim HW, Kang GCet al. . Long-lasting Ni-rich NCMA cathodes via simultaneous microstructural refinement and surface modification. ACS Energy Lett.. 2023, 8: 1354-1361.

[247] Kim JS, Jung S, Kwak Het al. . Synergistic halide-sulfide hybrid solid electrolytes for Ni-rich cathodes design guided by digital twin for all-solid-State Li batteries. Energy Storage Mater.. 2023, 55: 193-204.

[248] Yin SY, Chen HY, Chen Jet al. . Chemical-mechanical effects in Ni-rich cathode materials. Chem. Mat.. 2022, 34: 1509-1523.

[249] Xin FX, Goel A, Chen XBet al. . Electrochemical characterization and microstructure evolution of Ni-rich layered cathode materials by niobium coating/substitution. Chem. Mat.. 2022, 34: 7858-7866.

[250] Rathore D, Garayt M, Liu YLet al. . Preventing interdiffusion during synthesis of Ni-rich core–shell cathode materials. ACS Energy Lett.. 2022, 7: 2189-2195.

[251] Geng CX, Rathore D, Heino Det al. . Mechanism of action of the tungsten dopant in LiNiO₂ positive electrode materials. Adv. Energy Mater.. 2022, 12: 2103067.

[252] Zhang QM, Deng Q, Zhong WTet al. . Tungsten boride stabilized single-crystal LiNi_0.83Co_0.07Mn_0.1O₂ cathode for high energy density lithium-ion batteries: Performance and mechanisms. Adv. Funct. Mater.. 2023, 33. 2301336

[253] Ni LS, Chen HY, Guo Set al. . Enabling structure/interface regulation for high performance Ni-rich cathodes. Adv. Funct. Mater.. 2023, 33. 2307126

[254] Maiti S, Konar R, Sclar Het al. . Stabilizing high-voltage lithium-ion battery cathodes using functional coatings of 2D tungsten diselenide. ACS Energy Lett.. 2022, 71383-1391.

[255] Jamil S, Wang G, Yang Let al. . Suppressing H2–H3 phase transition in high Ni–low Co layered oxide cathode material by dual modification. J. Mater. Chem. A. 2020, 8: 21306-21316.

[256] Yu SA, Seo JK, Yun JMet al. . Hybrid surface coating layers comprising boron and phosphorous compounds on LiNi_0.90Co_0.05Mn_0.05O₂ cathode materials to ensure the reliability of lithium-ion batteries. Mater. Today Energy. 2023, 37: 101377.

[257] Yang HP, Wu HH, Ge MYet al. . Simultaneously dual modification of Ni-rich layered oxide cathode for high-energy lithium-ion batteries. Adv. Funct. Mater.. 2019, 29. 1808825

[258] Tan ZL, Li YJ, Xi XMet al. . Construction of planar gliding restriction buffer and kinetic self-accelerator stabilizing single-crystalline LiNi_0.9Co_0.05Mn_0.05O₂ cathode. ACS Appl. Mater. Interfaces. 2023, 158555-8566.

[259] Fan XM, Ou X, Zhao WGet al. . In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes. Nat. Commun.. 2021, 12. 5320

[260] Liu Y, Wang Q, Chen Let al. . Diffusion-induced stress optimization by boosted surface Li-concentration for single-crystal Ni-rich layered cathodes. Mater. Today. 2022, 61: 40-53.

[261] Zhang QM, Chu YQ, Wu JXet al. . Mitigating planar gliding in single-crystal nickel-rich cathodes through multifunctional composite surface engineering. Adv. Energy Mater.. 2024, 14: 2303764.

[262] Wang LF, Liu GC, Xu Ret al. . Enabling an intrinsically safe and high-energy-density 4.5 V-class lithium-ion battery with synergistically incorporated fast ion conductors. Adv. Energy Mater.. 2023, 132203999.

[263] Zhang R, Wang CY, Zou PCet al. . Long-life lithium-ion batteries realized by low-Ni, co-free cathode chemistry. Nat. Energy. 2023, 8695-702.

[264] Zhao C, Wang CW, Liu Xet al. . Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating. Nat. Energy. 2024, 9: 345-356.

[265] Dai ZS, Liu Y, Lu Xet al. . Ultra-high temperature operated Ni-rich cathode stabilized by thermal barrier for high-energy lithium-ion batteries. Adv. Mater.. 2024, 36. 2313500

[266] Dong QY, Wu JH, Wang YQet al. . Bifunctional self-assembled molecular layer enables stable Ni-rich cathodes. Energy Storage Mater.. 2023, 63. 103054

[267] Wandt J, Freiberg ATS, Ogrodnik Aet al. . Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries. Mater. Today. 2018, 21: 825-833.

[268] Sim R, Su LS, Manthiram AA. high energy-density, cobalt-free, low-nickel LiNi_0.7Mn_0.25Al_0.05O₂ cathode with a high-voltage electrolyte for lithium-metal batteries. Adv. Energy Mater.. 2023, 13: 2300096.

[269] Zhao LQ, Zhong YJ, Cao CCet al. . Enhanced high-temperature cycling stability of garnet-based all solid-state lithium battery using a multi-functional catholyte buffer layer. Nano-Micro Lett.. 2024, 16. 124

[270] Liu YC, Hong L, Jiang Ret al. . Multifunctional electrolyte additive stabilizes electrode–electrolyte interface layers for high-voltage lithium metal batteries. ACS Appl. Mater. Interfaces. 2021, 1357430-57441.

[271] Jiang B, Li JR, Luo Bet al. . LiPO₂F₂ electrolyte additive for high-performance Li-rich cathode material. J. Energy Chem.. 2021, 60: 564-571.

[272] Cheng FY, Xu J, Wei Pet al. . Interface engineering via regulating electrolyte for high-voltage layered oxide cathodes-based Li-ion batteries. Adv. Sci.. 2023, 10. 2206714

[273] Cao YJ, Li N, Yuan Ket al. . Revealing the mechanisms of electrolyte additive PTS on Ni-rich electrode: Tolerance to high temperature (50℃) and high voltage (4.6 V). Energy Storage Mater.. 2023, 60: 102851.

[274] Tan S, Shadike Z, Li JZet al. . Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V. Nat. Energy. 2022, 7484-494.

[275] Duan SH, Zhang SQ, Li Yet al. . H-transfer mediated self-enhanced interphase for high-voltage lithium-ion batteries. ACS Energy Lett.. 2024, 9: 3578-3586.

[276] Lu D, Lei XC, Weng STet al. . A self-purifying electrolyte enables high energy Li ion batteries. Energy Environ. Sci.. 2022, 15: 3331-3342.

[277] Zhang DF, Ma JB, Zhang Cet al. . A novel cathode interphase formation methodology by preferential adsorption of a borate-based electrolyte additive. Natl. Sci. Rev.. 2024, 11: 219.

[278] Ren ZQ, Qiu HY, Fan Cet al. . Delicately designed cyano-siloxane as multifunctional additive enabling high voltage LiNi_0.9Co_0.05Mn_0.05O₂/graphite full cell with long cycle life at 50 ℃. Adv. Funct. Mater.. 2023, 33. 2302411

[279] Hong LX, Zhang Y, Mei Pet al. . Temperature-responsive formation cycling enabling LiF-rich cathode-electrolyte interphase. Angew. Chem. -Int. Edit.. 2024, 63. e202409069

[280] Han Y, Jung SH, Kwak Het al. . Single- or poly-crystalline Ni-rich layered cathode, sulfide or halide solid electrolyte: Which will be the winners for all-solid-state batteries?. Adv. Energy Mater.. 2021, 112100126.

[281] Dai ZS, Li ZJ, Chen RJet al. . Defective oxygen inert phase stabilized high-voltage nickel-rich cathode for high-energy lithium-ion batteries. Nat. Commun.. 2023, 14. 8087

[282] Cui BC, Xiao ZX, Cui SLet al. . Safety issues and improvement measures of Ni-rich layered oxide cathode materials for Li-ion batteries. Electrochem. Energy Rev.. 2024, 7. 27

[283] Shen X, Zhang R, Chen Xet al. . The failure of solid electrolyte interphase on Li metal anode: Structural uniformity or mechanical strength?. Adv. Energy Mater.. 2020, 101903645.

[284] Xiao YR, Yang L, Zeng CYet al. . Suppressing high voltage chemo-mechanical degradation in single crystal nickel-rich cathodes for high-performance all-solid-state lithium batteries. J. Energy Chem.. 2025, 102377-385.

[285] Xu ZH, Wang XH, Wang ZYet al. . Interface problems, modification strategies and prospects of Ni–rich layered oxide cathode materials in all-solid-state lithium batteries with sulfide electrolytes. J. Power Sources. 2023, 571. 233079

[286] Park NY, Lee HU, Yu TYet al. . High-energy, long-life Ni-rich cathode materials with columnar structures for all-solid-state batteries. Nat. Energy. 2025, 10: 479-489.

[287] Zhao H, Lam WA, Sheng Let al. . Cobalt-free cathode materials: Families and their prospects. Adv. Energy Mater.. 2022, 122103894.

Funding

National Natural Science Foundation of China(52064049)

Major Science and Technology Projects in Yunnan Province(202302AB080019-3)

Natural Science Foundation of Yunnan Province(202301AS070040)

Yunnan Provincial Department of Education Science Research Fund Project(2023J0033)

Postgraduate Research and Innovation Foundation of Yunnan University(KC-23236292)

RIGHTS & PERMISSIONS

The Author(s)